JPS5837439B2 - fiber sizing agent - Google Patents

Description

[Detailed description of the invention] The present invention relates to fiber sizing agents.

More specifically, the present invention relates to a home-use sizing agent that provides appropriate hardness to clothing when continuous or intermittent stirring force is applied to the clothing with a bath liquid having a high bath ratio.

Starch has traditionally been used as a household sizing agent, but various improvements have been made to make it easier to use.Currently, liquid sizing agents are available as stable sizing agents that are easy to dilute in cold water, easy to use, and convenient. has been developed, and a 10 to 15% aqueous solution of carboxymethyl cellulose, starch, polyvinyl alcohol, etc. is mixed with an antifoaming agent, an antifungal agent, a fluorescent whitening agent, a fragrance, and the like.

In use, water is placed in a container, these sizing agents are dispersed or dissolved, and clothing is immersed and left to stand for sizing.

The amount of water used at this time is usually 1 part per weight of clothing.
It is about 3 times as much, and if a large amount of water is used, the sizing agent will be used in vain, which is uneconomical.

Different types of clothing require different degrees of starching; for example, sheets, futon covers, etc. require crisp hardness.

On the other hand, for shirts, blouses, etc., the collar and cuffs are required to be hard and the body part must be soft and glued.

Currently, there are many polyester/cotton blend wash-and-air dress shirts, blouses, etc. that are made of polyester/cotton blends at home, but these are glued by spraying a special aerosol glue on areas such as collars and cuffs after washing. The trouble of processing has become a problem, and there has been a desire for a new development that would allow for the appropriate amount of glue to be applied when washing, but there is currently no suitable product.

The present invention provides a sizing agent that imparts appropriate hardness to clothing such as shirts and blouses, especially to wash-and-air clothing when they are washed.

The sizing agent of the present invention is a polymer emulsion obtained by emulsion polymerization of a vinyl monomer in the coexistence of a cationic polymer and a nonionic water-soluble polymer, and the cationic nitrogen content derived from the cationic polymer is is 0.00 relative to total solids
It contains a polymer emulsion having a weight of 4 to 0.2, and the sizing agent of the present invention is applied to the clothes by using 10 to 100 times the amount of water, preferably 15 to 40 times the amount of water to the clothes. By adding 0.2 to 3 weight of starch, preferably 0.4 to 2 weight of starch, and applying continuous or intermittent stirring to make the sizing agent adhere to the clothes, appropriate hardness can be imparted to the clothes. I can do it.

The vinyl polymer emulsion used in the present invention is obtained by emulsion polymerization of vinyl monomers in a nonionic water-soluble polymer aqueous solution in the presence of a cationic polymer.

Examples of the nonionic water-soluble polymer used in the present invention include polyvinyl alcohol obtained by saponifying 70 to 100% of polyvinyl acetate, modified starches such as hydroxyethylated starch, hydroxyglopylated starch, hydroxyethyl cellulose, and hydroxypropyl cellulose. Examples include derivatives, and among these, 1% aqueous solution viscosity is 3 to 500 centipoise (hereinafter abbreviated as cps), preferably 5 to 100 Cp.
s is good.

Examples of the cationic polymer used in the present invention include cationic cellulose or cationic starch (particularly preferred are water-soluble polymers whose cation group is a quaternary ammonium cation group), or a cationic vinyl polymer.

As the cationic starch or cationic cellulose, for example, those represented by the following formula (4) are preferable.

The degree of cation substitution of cationic cellulose or cationic starch is 0.01 to 1, ie 0.0.
01-1, preferably 0.02-0.5 cationic groups are introduced.

A degree of substitution of 0.01 or less is not sufficient, and a degree of 1 or more is acceptable, but from the viewpoint of reaction yield, 1 or less is preferable.

In addition, as a cationic vinyl polymer, the following formula (support) ~ (
4) is exemplified.

The viscosity of an aqueous solution of a cationic polymer is 5 as a 1% aqueous solution.
~1000Cps (20°C), preferably 10-5
0 0 cps is good.

The amount of cationic polymer added when obtaining the vinyl polymer emulsion of the present invention is 0 to the total emulsion system.
．． 0.01 to 5 weight, preferably 0.2 to 3 weight.

The cationic nitrogen content derived from the cationic polymer contained in the polymer emulsion is 0.0 based on the total solid content.
04 to 0.2 weight, preferably 0.01 to 0.15
It is a heavy robe.

If the weight is less than 0.004 φ, the effect will not be sufficient;
．． If it is 2 weight φ or more, it is good in terms of performance, but it causes coloring of the vinyl polymer emulsion and is also economically disadvantageous.

Vinyl acetate is the best vinyl monomer used to obtain the vinyl polymer emulsion according to the present invention.
Examples include lower fatty acid vinyl esters such as vinyl acetate and vinyl propionate; acrylic esters such as methyl acrylate, ethyl acrylate, and butyl acrylate; and methacrylic esters such as methyl methacrylate, ethyl methacrylate, and butyl methacrylate.

Furthermore, monomers copolymerizable with these monomers, such as styrene and ethylene, can also be used at the same time.

The amount of monomer used is 20 to 60% of the final emulsion.
A weight rice cake, preferably 25 to 50 weight φ is good.

When obtaining the vinyl polymer emulsion according to the present invention, a nonionic surfactant can be added as an emulsifier if necessary.

Typical examples include polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether,
Examples include polyoxyethylene sorbitan fatty acid ester.

These nonionic surfactants preferably have an HLB II or higher, and more preferably have an HLB of 13 to 18.

The best polymerization initiator for obtaining the vinyl polymer emulsion according to the present invention is 2,2'-azobis(2-amidinopropane), but others include hydrogen peroxide, t-butyl hydroperoxide, and cumene hydroperoxide. , t-butyl peroxide, methyl ethyl ketone peroxide, cyclohexanone peroxide, peracetic acid, perbenzoic acid, and the like can also be used.

The amount of these polymerization initiators added is 0.0 per vinyl monomer.
It is preferable to use it within the range of 1 to 5.0 weight φ.

The reaction temperature for obtaining the vinyl polymer emulsion of the present invention is 40 to 120°C, preferably 50 to 90°C, and I
)H is 3-9, preferably 4-8.

In this case, pE {Buffers include inorganic salts such as sodium carbonate, sodium bicarbonate, sodium orthophosphate, dibasic sodium phosphate, monobasic sodium phosphate, sodium chloride, and sodium sulfate, or organic acids such as sodium acetate. It is advisable to add salt in an amount of 0.05 to 2 weight, preferably 0.1 to 1 weight.

The sizing agent of the present invention may further contain additives for general polymer emulsions, such as plasticizers such as dibutyl phthalate, dibutyl adipate, dioctyl adipate, triacetin, etc., and freezing agents such as ethylene glycol, propylene glycol, and ethanol. Inhibitors, other fragrances, fungicides, preservatives, fluorescent dyes, pigments, etc. can be added.

When using the sizing agent of the present invention, it is also possible to use a method using a conventional sizing agent, that is, a method in which the amount of water used to dilute the sizing agent for clothing, the so-called bath ratio, is about 1=1 to 1:4. However, for most effective use the bath ratio should be between 1210 and 1:100, preferably between 1:15 and 1:40.
It is best to use it as

Such an increase in the bath ratio enables uniform sizing.Moreover, when used at home, continuous strong agitation force, such as in an electric washing machine, is applied to fluidize the sizing agent aqueous solution and make it stick. Although it adsorbs well to thin materials, it has the effect of being less adsorbable to thin materials.

Therefore, it has very good adsorption properties for thick fabrics such as sheets, while for garments such as dress shirts and blouses, the adsorption properties of the glue on single layers of fabric such as the body area are limited to the collar,
The amount of adhesive adsorbed is smaller than that of the sizing agent on double fabric or interlining parts such as cufflinks, and the finishing effect is superior to conventional ones.

This finishing effect could not be achieved with conventional sizing agents that are nonionic or anionic.
Increasing the bath ratio and imparting stirring power have no meaning in conventional sizing agents.

The stirring force when using the sizing agent of the present invention may be such that continuous or intermittent stirring mechanical force is applied to the sizing agent aqueous solution. It is convenient to use a washing machine with an agitator or tumbler set.

When sizing using the sizing agent of the present invention, the ratio of sizing agent to clothing weight is 0.2 to 3 weight of sizing agent effective content (solid content) to clothing weight, preferably 0.4 to 2 weight φ
It is.

Hereinafter, specific examples of the present invention will be described in detail, but the present invention is not limited to these examples.

Parts in the examples are parts by weight.

Example 1 [Synthesis of hinyl polymer emulsion] x parts of polyvinyl alcohol (completely saponified, degree of polymerization 1800) and 130 parts of ion-exchanged water was added and dissolved at 80°C.

After cooling to 40°C, trinotylaminohydride was added to the pylated starch. Degree of cation substitution (average value of the number of cationic groups introduced per unit of anhydroglucose): 0.30, 1% aqueous solution viscosity: 30 centipoise} y parts , 0.5 part of polyoxyethylene dodecyl ether (average number of added moles of ethylene oxide: 30 moles) and an aqueous sodium carbonate solution of 1 part of sodium carbonate and 10 parts of ion-exchanged water are added, and the air in the flask is replaced with nitrogen.

Next, 10 parts of vinyl acetate monomer was added, and an additional 2,2'
A polymerization initiator consisting of 0.1 part of -azobis(2-amidinopropane) hydrochloride and 10 parts of ion-exchanged water was added, and the temperature was raised to 70°C to initiate polymerization.

Vinyl acetate monomer 901 was continuously added for 100 minutes from 10 minutes after the start of polymerization.

After the continuous addition was completed, the mixture was aged at 80° C. for 1 hour to complete the emulsion polymerization reaction.

[Manufacture of glue]

Add 2 parts of dibutyl adipate, 4 parts of ethanol, and silicone emulsion to 90 parts of the emulsion that was combined earlier.
iooo centistoke silicone oil 30% emulsion) and 3.5 parts of ion-exchanged water were added to prepare a sizing agent.

[Gluing test]

Using a tergotometer-type cleaning tester, add 0.6 F of sizing agent to 1,000 fresh ion-exchanged water, disperse well, add 50.9 amounts of cotton cloth (60Φ), and rotate at 10 O. Stir and glue for 3 minutes at rpm.

After dehydrating for 30 seconds in a dehydrator (dehydration tank of a national washing machine), air dry, ainin press (1 minute at 130℃),
After storing for 1 day in a constant temperature room at 20'C, JIS-10
Tensile hardness (the larger the number, the harder) was measured by the cantilever method in accordance with 05-1959.

Table 1 shows the evaluation results of sizing agents synthesized with various amounts of polyvinyl alcohol and trimethylaminohydroxyprobylated starch.

Sizing agent composition A, which is outside the scope of the present invention, was treated in the same manner with the addition of three times the amount of the effective sizing agent, that is, 1.8 g, but the tension hardness increased only to 6.2 crIL.

Example 2 5.2 parts of polyvinyl alcohol (completely saponified, degree of polymerization 11,800) and 130 parts of ion-exchanged water were added to a five-piece separable flask equipped with a thermometer, stirrer, reflux condenser, nitrogen introduction device, and quantitative dropping device. In addition, it was dissolved at 80°C.

After cooling to 40°C, dimethylaminohydride was added to the pylated starch. Degree of cation substitution (average number of cationic groups introduced per unit of anhydroglucose): 0.6, 1% aqueous solution viscosity: 3
0 centipoise} 7.8 parts, or trinotylaminohydroxyethylated starch cation substitution degree 0.6.1% aqueous solution viscosity 35 centipoise} 7.8 parts, and polyoxyethylene stearyl ether (average addition of 25 moles of ethylene oxide) 0,5
A sodium carbonate aqueous solution of 1 part of sodium carbonate and 10 parts of ion-exchanged water is added, and the air in the flask is replaced with nitrogen.

Next, 10 parts of vinyl acetate monomer were added, and a polymerization initiator consisting of 0.1 part of 2,2'-azobis(2-amidinopropane) hydrochloride and 10 parts of ion-exchanged water was added, and the temperature was raised to 70°C to initiate polymerization.

90 parts of vinyl acetate monomer was continuously added over 100 minutes starting 10 minutes after the start of polymerization.

After the continuous addition was completed, the mixture was aged at 80° C. for 1 hour to complete the emulsion polymerization reaction.

90 parts of this emulsion, 2 parts of dibutyl adipate, 4 parts of ethanol, 0 silicone emulsion (10,000 centistoke silicone oil, 30% emulsion)
．． 5 parts and 3.5 parts of ion-exchanged water were added to prepare a sizing agent.

The sizing agent thus obtained was heated to -10°C to 5°C (-10°C
As a result of storage at 40°C for 1 month, the product of the present invention, trimethylaminohydroxyethylated starch, showed no change in the sizing composition. Although no change occurred, the dimethylaminohydroxyprobylated starch-based sizing composition separated into two layers under both conditions.

Example 3 Comparison of the gluing performance (stretching hardness) of Example 1-J glue composition and a commercially available nonionic vinyl acetate emulsion based glue on a 60" cotton cloth using the same method as in Example 1. The results are shown in Table 2.

Example 4 According to Example 1, using the same experimental equipment, polyvinyl alcohol (polyvinyl acetate saponification degree 78.5%, polymerization degree 16)
00) and 130 parts of ion-exchanged water were added and dissolved at 80°C.

After cooling to 40℃, cationic cellulose { J R
-4 0 0 , Union Carbide Comp
Company manufactured by Hydroxyethyl substitution degree (average value of the number of hydroxyethyl groups introduced per unit of anhydroglucose)
1.6 to 2.1, degree of cation substitution 0.35 to 0.45,
Nitrogen content: 1.7 to 2.2 pieces} 0.3 parts, 0.8 parts of holoxyethylene nonyl phenyl ether (average 20 moles of ethylene oxide added), 0.5 parts of soda carbonate, and 5 parts of ion-exchanged water. Add aqueous sodium carbonate solution and replace the air in the flask with nitrogen.

Next, 10 parts of vinyl acetate monomer was added, and a polymerization initiator of 0.1 part of 2,2'-azobis(2-amidinofuropane) hydrochloride and 10 parts of ion-exchanged water was added, and the temperature was raised to 70°C to start polymerization. did.

90 parts of vinyl acetate monomer was continuously added over 100 minutes starting 10 minutes after the start of polymerization.

After the continuous addition was completed, the mixture was aged at 80° C. for 1 hour to complete the emulsion polymerization reaction.

The solid content concentration is 42.4% and the particle size is approximately 0.5-1.0
It was μ.

To 91 parts of this emulsion, 2 parts of dibutyl phthalate,
A sizing agent was prepared by adding 3 parts of ethanol, 2 parts of propylene glycol, 0.5 part of a silicone emulsion (30% emulsion of 10,000 centigrade silicone oil), and 1.5 parts of ion-exchanged water.

This sizing agent exhibited useful properties as a sizing agent using a washing machine.

Example 5 8 parts of polyvinyl alcohol (completely saponified, degree of polymerization 1800) and 130 parts of ion-exchanged water were added to a 5-piece separable flask equipped with a thermometer, stirrer, reflux condenser, nitrogen introduction device, and quantitative dropping device. It was dissolved at 80°C.

After cooling to 40°C, trinotylaminopropylated starch (degree of substitution 0.5, 1% aqueous solution viscosity 45 centipoise) O
, 5 parts of polyoxyethylene stearyl ether (average 25 moles of ethylene oxide added), 0.5 parts of polyoxyethylene stearyl ether (average addition of 25 moles of ethylene oxide), and an aqueous sodium carbonate solution of 1 part of sodium carbonate and 10 parts of ion-exchanged water are added, and the air in the flask is replaced with nitrogen.

Next, a polymerization initiator consisting of 10 parts of vinyl acetate monomer, 0.1 part of 2,2'-azubis(2-amidinopropane) hydrochloride, and 10 parts of ion-exchanged water was added, and the temperature was raised to 70°C to initiate polymerization.

90 parts of vinyl acetate monomer was continuously added over 100 minutes starting 10 minutes after the start of polymerization.

After the continuous addition was completed, the mixture was aged at 80°C for 1 hour to complete the emulsion polymerization reaction.

The diameter of this emulsion was measured using an optical microscope, and the average particle diameter was approximately 0.7 μm.

Moreover, the solid content concentration was 44.9%.

90 parts of this emulsion, 2 parts of dibutyl adipate, 4 parts of ethanol, 0 silicone emulsion (ioooo centistoke silicone oil, 30% emulsion)
．． 5 parts and 3.5 parts of ion-exchanged water were added to prepare a sizing agent.

This sizing agent is used for sizing using a washing machine (not only does it give hard tension to sheets and futon bars, but it also gives a relatively soft feel to the body of shirts and blouses, and a crisp texture to collars, cuffs, etc.). Ta.

Claims (1)

[Scope of Claims] 1. A polymer emulsion obtained by emulsion polymerization of a vinyl monomer in the coexistence of a cationic polymer and a nonionic water-soluble polymer, which contains cationic nitrogen derived from the cationic polymer. A fiber sizing agent comprising a polymer emulsion in an amount of 0.004 to 0.2 weight φ based on the total solid content. 2. The fiber sizing agent according to claim 1, wherein the cationic polymer is cationic cellulose or cationic starch. 3. The fiber sizing agent according to claim 2, wherein the cationic polymer has a degree of cation substitution of 0.01 to 1.0. 4. The fiber sizing agent according to claim 1, wherein the cationic polymer is a cationic vinyl polymer represented by the following formula. 5. The fiber sizing agent according to claim 1, wherein the cationic polymer is a cationic vinyl polymer represented by the following formula. 6. The fiber sizing agent according to claim 1, wherein the cationic polymer is a cationic vinyl polymer represented by the following formula. 7. The fiber sizing agent according to claim 1, wherein the cationic nitrogen content derived from the cationic polymer of the polymer emulsion is 0.01 to 0.15 weight φ based on the total solid content. 8. The fiber sizing agent according to claim 1, wherein the nonionic water-soluble polymer is a modified starch, hydroxyethyl cellulose, or hydroxybutylated cellulose. 9 Nonionic water-soluble polymer has saponification degree of 70 to 100
% of polyvinyl alcohol. 10 The vinyl monomer is selected from vinyl acetate monomer, acrylic methyl monomer, methyl methacrylate monomer, or a mixture thereof, or a mixture of these with ethylene monomer or styrene monomer. A sizing agent according to claim 1, which is a sizing agent. 11 A polymer emulsion obtained by emulsion polymerization of a vinyl monomer in the coexistence of a cationic polymer and a nonionic water-soluble polymer, the cationic nitrogen content of which is 0.004 to 0 based on the total solid content. . A method of sizing fibers in the presence of stirring mechanical force in a water diluted solution of a fiber sizing agent containing a polymer emulsion of 2 wt.